JP4957550B2 - Adhesive composition, adhesive sheet using the same, and use thereof - Google Patents

Description

The present invention particularly relates to an adhesive composition for a flexible printed wiring board having a polyimide film or the like as a base film on which a semiconductor integrated circuit (IC) or the like is mounted, an adhesive sheet for a flexible printed wiring board, and the like. The present invention relates to various flexible printed wiring boards and manufacturing methods thereof.
Specifically, an adhesive composition for fixing a reinforcing material made of metal, glass epoxy, polyimide, or the like to a flexible printed wiring board, an adhesive sheet, and a cover film for attaching to the conductive circuit side of the flexible printed wiring board. Adhesive composition, adhesive composition and adhesive sheet suitable for further laminating flexible printed wiring boards, and further laminating using the adhesive composition, for adhesiveness and soldering heat resistance The present invention relates to various excellent flexible printed wiring boards.

A flexible printed wiring board whose amount of use as a printed wiring board has been increased is that a conductive circuit is provided on a base film by various methods.
As a method for providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper-clad plate in which a copper foil is provided on a base film with or without an adhesive layer. Expose the conductive circuit from the copper foil by exposing it through a mask film with a pattern, curing only the exposed area, then removing the unexposed area of the copper foil by etching, and then peeling off the remaining resist layer. Can be formed. Alternatively, only a necessary circuit may be provided on the base film by means such as sputtering or plating.

  In general, as a flexible printed wiring board, one having a conductive circuit on one surface, one having a conductive circuit on both surfaces, and one having a conductive circuit inside thereof are used. In addition, as the base film, a plastic film having insulating properties, flexibility, and heat resistance, for example, a film of polyimide or polyethylene terephthalate (PET) is generally used. As the copper foil, an electrolytic copper foil is used. Alternatively, rolled copper foil is generally used.

Here, various adhesives are used for the flexible printed wiring board.
For example,
An adhesive for forming a flexible copper-clad plate by bonding a copper foil and a base film for forming a conductive circuit,
An adhesive for attaching a reinforcing material to a portion of the flexible printed circuit board where the conductive circuit is not provided,
An adhesive for affixing a cover film for covering the side on which the conductive circuit of the flexible printed wiring board is provided;
Furthermore, an adhesive for laminating a plurality of flexible printed wiring boards and laminating a plurality of conductive circuit layers can be used.

  In the present specification, the “part where the conductive circuit is not provided” of the flexible printed wiring board is the surface opposite to the surface where the conductive circuit of the flexible printed wiring board is provided, Means a surface on which the circuit is not formed, on the same surface as the surface on which the conductive circuit of the flexible printed wiring board is provided.

Furthermore, as other uses of adhesives in printed wiring boards,
Adhesive to bond the package substrate necessary for the manufacture of ball grid array (BGA), which is a semiconductor package with excellent weight reduction, cost reduction, and reinforcement plate (stiffener) and heat sink (heat spreader),
Examples thereof include an adhesive for affixing an electromagnetic shielding material or the like to the device casing.

  Flexible printed wiring boards, which are increasingly used as wiring boards, are weak and susceptible to physical damage, so some of the wiring boards may be reinforced with reinforcing materials to increase mechanical strength. . For example, a reinforcing material is bonded to a portion where stress is concentrated, such as a terminal portion inserted into a socket and a switch portion.

  Also, in order to protect the conductive circuit on the flexible printed wiring board, to prevent oxidation, and to improve the flexibility of the conductive circuit, the conductive circuit surface is generally a protective and covering plastic through an adhesive layer. The film is coated. (This plastic film is also called “cover film”.)

In addition, as electronic devices become more compact and more dense, the demand for multilayer printed wiring boards having a plurality of conductive circuit layers that can be efficiently wired in a narrow space is increasing. There is an increasing demand for a printed wiring board in which a plurality of flexible printed wiring boards are bonded and a plurality of conductive circuits are laminated.
Most of the interlayer adhesive materials used in current multilayer printed wiring boards are thermosetting resin prepregs in which a base material such as glass cloth is impregnated with a thermosetting resin typified by an epoxy resin. However, in recent years, with the reduction in thickness and density of multilayer printed wiring boards, there has been an increasing demand for interlayer adhesive materials that do not use a substrate such as glass cloth in order to extremely narrow the interval between each printed wiring board to be laminated. .

A polyimide film is often used for a plastic film serving as a base of the flexible printed wiring board, a cover film for surface protection, or a BGA package substrate because of its good heat resistance. In addition, as a reinforcing material for flexible printed wiring boards, stiffeners, heat spreaders, or electromagnetic wave shielding materials used for BGA, metal materials such as glass epoxy plates and stainless steel plates (for example, SUS plates), polyimide films, etc. Often used.
Therefore, polyimide film and glass epoxy board, polyimide film and metal plate, and polyimide films are good for adhesives used in these applications and adhesives for laminating and laminating flexible printed wiring boards. It is required to be adhered to.

  After a reinforcing material or cover film is attached to the flexible printed wiring board, or a printed wiring board is produced by laminating a plurality of flexible printed wiring boards, and the reinforcing material or cover film is also attached, an electronic device is mounted on the wiring board. Parts are mounted.

As a method of mounting electronic components on the wiring board, the entire wiring board including the solder portion formed by printing or coating in advance is heated to about 230 to 280 ° C. by infrared reflow, etc., and the solder is melted to bond the electronic components to the wiring board. Many methods (solder reflow) are used. In addition, a method of attaching a cover film so that a part of the conductive circuit of the printed wiring board is exposed, and bringing molten solder into contact with the exposed conductive circuit portion is also employed.
Therefore, the adhesive used in the various applications mentioned above has heat resistance that does not cause foaming / peeling due to solder reflow, and high heat resistance that does not cause foaming / peeling even when in contact with molten solder. Is required.

  Printed wiring boards are key components in the electronics field, where the market is growing rapidly, and their manufacturing and processing bases are scattered throughout the country. Therefore, printed wiring boards and materials for producing them are desired to have excellent storage stability with little property change even after transport and storage processes under various conditions.

  At present, the adhesive used for the above-mentioned applications related to the production of printed wiring boards, for example, using a mixture of an epoxy resin and an epoxy resin curing agent as a curing component, to give an improvement in peel strength and flexibility. In addition, an epoxy resin composition containing a flexible component such as acrylonitrile butadiene rubber is widely used (see, for example, Patent Document 1). Such an epoxy resin-based composition has high heat resistance and good substrate adhesion, but a majority of the composition is occupied by the epoxy resin and its curing agent, and the epoxy resin is in a semi-cured state (B stage). ) In many cases. Therefore, it needs to be stored at a low temperature, and has a problem of poor storage stability.

  Moreover, the acrylic resin type composition which mix | blended the epoxy resin as a hardening component using the acrylic resin for a base polymer is proposed (for example, refer patent document 2 and patent document 3). These contain functional groups capable of cross-linking with epoxy resins in acrylic resins, and since substantially no epoxy resin curing agent is used, a composition that has good storage stability and adheres well to metal materials is obtained. However, there is a problem that the adhesion to the polyimide film is not yet sufficient.

  In addition, a method has been proposed in which a saturated polyester resin is used in combination to improve the storage stability by relatively reducing the curing component and to adjust the degree of curing, but there is a problem that solder heat resistance is reduced (for example, , Patent Document 4 and Patent Document 5).

  In addition, an adhesive composition containing an epoxy adhesive as the main component and a urethane prepolymer composed of diol and diisocyanate and a diamine curing agent has excellent copper foil / polyimide adhesive strength and good soldering heat resistance. It has been proposed to have sex. In this adhesive composition, a diamine compound as a curing agent reacts with both an epoxy resin and a urethane prepolymer to obtain good heat resistance, but an isocyanate group and a diamine curing agent which are functional groups of the urethane prepolymer. It is difficult to achieve both storage stability and solder heat resistance (see Patent Document 6).

  Furthermore, an adhesive composition containing a resin containing a urethane bond and / or a urea bond in the main chain and a thermosetting resin is also known (Patent Document 7). However, the resin containing a urethane bond and / or a urea bond in the main chain disclosed in Patent Document 7 does not have a carboxyl group. Therefore, even if an epoxy resin is used as the thermosetting resin, no reaction occurs between the two resins, so that the solder heat resistance is poor. In particular, the solder heat resistance after humidification is significantly reduced.

JP-A-4-370996 JP-A-9-316398 JP 2002-12841 A JP-A-6-330014 Japanese Unexamined Patent Publication No. 2000-273430 JP-A-8-32230 Japanese Patent Laid-Open No. 10-178066

  The present invention solves the problems of conventional adhesive compositions for flexible printed wiring boards and various constituent materials for printed wiring boards using the same, polyimide film, conductive circuit, and Adhesive composition having excellent adhesive strength to reinforcing material, good storage stability, and capable of obtaining a cured layer having excellent soldering heat resistance, and also a printed wiring obtained using the adhesive composition It aims at providing the various structural material for board.

According to the present invention, the above-mentioned problem is achieved by the urethane prepolymer (d) having an isocyanate group obtained by reacting the polyol compound (a), the organic diisocyanate (b) and the diol compound (c) having a carboxyl group, and a polyamino compound. A polyurethane polyurea resin (A) and an epoxy resin having a weight average molecular weight of 80000 to 250,000 and an acid value of 3 to 25 mg KOH / g, obtained by reacting (e) and the monoamino compound (f) under the following conditions: It can be solved by the adhesive composition (I) characterized by containing B).
(I) The ratio of the isocyanate group of the urethane prepolymer (d) having an isocyanate group to the amino group of the polyamino compound (e) and the monoamino compound (f) is amino group / isocyanate group = 0.8 / 1 to 0. 999/1 (molar ratio),
And,
(Ii) The ratio of the amino group of the polyamino compound (e) is 90.0 to 97.0 mol% in a total of 100 mol% of the amino group of the polyamino compound (e) and the amino group of the monoamino compound (f).

  Moreover, in the preferable aspect of the said adhesive composition (I) of this invention, the urethane prepolymer (d) which has an isocyanate group, The hydroxyl group of the diol compound (c) which has a polyol compound (a) and a carboxyl group, The organic diisocyanate (b) is reacted in a ratio of isocyanate group / hydroxyl group = 1.05 / 1 to 1.50 / 1 (molar ratio) with an isocyanate group.

  Moreover, in the preferable aspect of the said adhesive composition (I) of this invention, the amine value of a polyurethane polyurea resin (A) is 0-1.5 mgKOH / g.

  In a preferred embodiment of the adhesive composition (I) of the present invention, the polyol compound (a) has a number average molecular weight of 1000 to 5000, and the urethane prepolymer (d) has a weight average molecular weight of 10,000 to 10,000. 50000.

  Moreover, in the preferable aspect of the said adhesive composition (I) of this invention, 5-100 weight part of epoxy resins (B) are contained with respect to 100 weight part of polyurethane polyurea resins (A).

  Moreover, in the preferable aspect of the said adhesive composition (I) of this invention, a filler (C) is contained, and especially filler (C) 0.1 with respect to 100 weight part of polyurethane polyurea resins (A). Contains ~ 100 parts by weight.

  Moreover, this invention relates to the adhesive sheet which has curable adhesive bond layer (II) which consists of said adhesive composition (I) on a peelable sheet.

  Moreover, in the preferable aspect of the said adhesive agent sheet of this invention, it has another peelable sheet | seat on curable adhesive bond layer (II).

  Moreover, this invention relates to the reinforcing material with an adhesive layer for flexible printed wiring boards which has curable adhesive layer (II) formed from said adhesive composition (I) on a reinforcing material.

  In the present invention, the reinforcing material is fixed to the portion of the flexible printed wiring board where the conductive circuit is not provided via the cured adhesive layer (III) formed from the adhesive composition (I). The present invention relates to a flexible printed wiring board with a reinforcing material.

  Moreover, this invention relates to the manufacturing method of the flexible printed wiring board with a reinforcing material characterized by fixing a reinforcing material to a flexible printed wiring board using said adhesive agent sheet.

  In addition, the present invention provides the above-mentioned adhesive composition (I) on a reinforcing material to provide a curable adhesive layer (II), and then the curable adhesive layer (II) is a flexible printed wiring. It is related with the manufacturing method of the flexible printed wiring board with a reinforcement characterized by heating, after making it contact and stick to the part in which the conductive circuit of a board is not provided, and / or making it contact and stick.

  The present invention also relates to a plastic with an adhesive layer in which a curable adhesive layer (II) comprising the above-mentioned adhesive composition (I) is sandwiched between a plastic film that has not been peeled off and a protective film. Related to film.

  Further, the present invention provides a conductive circuit side surface of a flexible printed wiring board having a conductive circuit on the surface, through a cured adhesive layer (III) formed from the above-mentioned adhesive composition (I), The present invention relates to a flexible printed wiring board with a cover film, which is covered with a plastic film that has not been subjected to a peeling treatment.

  In addition, the present invention provides a surface on the conductive circuit side of a flexible printed wiring board having a conductive circuit on the surface by peeling off the protective film from the above-mentioned plastic film with an adhesive layer and exposing the exposed curable adhesive layer (II). It is related with the manufacturing method of the flexible printed wiring board with a cover film characterized by heating, after making it contact and stick and / or making it contact and stick.

  In the present invention, the adhesive composition (I) is applied to one surface of a plastic film that has not been peeled to form a curable adhesive layer (II), and then the curable adhesive. It is characterized by heating the layer (II) while the surface on the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface is brought into contact and / or stuck and then brought into contact and stuck. The present invention relates to a method for manufacturing a flexible printed wiring board with a cover film.

  In the present invention, the adhesive composition (I) is applied to the surface on the conductive circuit side of a flexible printed wiring board having a conductive circuit on the surface to form a curable adhesive layer (II). Then, the flexible film with a cover film is characterized in that the curable adhesive layer (II) is heated by contacting and adhering a non-peeled plastic film and / or contacting and adhering. The present invention relates to a method for manufacturing a printed wiring board.

In addition, the present invention, through the cured adhesive layer (III) formed from the above adhesive composition (I),
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. Whether the surface of the conductive circuit is attached or
Is one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides and the surface on the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface? ,
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. Is it bonded to the surface where the conductive circuit is not provided?
One surface of the double-sided printed wiring board (2) having a conductive circuit on both sides and the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are not provided. Or
Whether one surface of the first double-sided printed wiring board (2) having the conductive circuit on both sides and one surface of the second double-sided printed wiring board (2) having the conductive circuit on both sides are bonded together Or
A surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, where no conductive circuit is provided, and a second single-sided printed wiring board having a conductive circuit only on one surface ( It relates to a printed wiring board formed by laminating a plurality of conductive circuit layers, which is bonded to a surface on which a conductive circuit of 1) is not provided.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface is not attached to the exposed curable adhesive layer (II), the surface is not attached. And / or heating after contacting and sticking,
Or
Remove one peelable sheet from the above adhesive sheet, and expose the exposed curable adhesive layer (II).
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the other peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Or
Remove one peelable sheet from the above adhesive sheet, and expose the exposed curable adhesive layer (II).
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
The exposed curable adhesive layer (II) is brought into contact with and / or brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. The present invention relates to a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is carried out after pasting.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
Contact with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, where the conductive circuit is not provided, and then peel off the other peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Or
Remove one peelable sheet from the above adhesive sheet, and expose the exposed curable adhesive layer (II).
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
Adhering the exposed surface of the curable adhesive layer (II), which is not provided with the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
Adhering and / or adhering one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides to the exposed curable adhesive layer (II) Then, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

Moreover, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (II).
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the other peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface is not provided in contact with the exposed curable adhesive layer (II), the surface is not attached. In addition, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contacting and sticking.

The present invention also provides the above-mentioned adhesive composition (I),
Applying to the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, forming a curable adhesive layer (II),
Next, on the curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board ( 1) A plurality of conductive circuit layers, wherein a surface not provided with a conductive circuit is contacted and adhered and / or heated after contacting and pasting, is laminated It is related with the manufacturing method of the printed wiring board which becomes.

The present invention also provides the above-mentioned adhesive composition (I),
It is applied to the surface on the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and a curable adhesive layer (II) is formed.
Then, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (II) and / or after making contact and sticking, Heating or
Or
The above-mentioned adhesive composition (I)
Apply to one surface of double-sided printed wiring board (2) with conductive circuit on both sides to form curable adhesive layer (II),
Next, the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface is brought into contact with and / or adhered to the curable adhesive layer (II). It is related with the manufacturing method of the flexible printed wiring board by which a several electroconductive circuit layer is laminated | stacked characterized by heating after sticking.

The present invention also provides the above-mentioned adhesive composition (I),
Apply to one surface of double-sided printed wiring board (2) with conductive circuit on both sides to form curable adhesive layer (II),
Next, the surface of the single-sided printed wiring board (1) having a conductive circuit on only one surface thereof, which is not provided with the conductive circuit, is brought into contact with and adhered to the curable adhesive layer (II) and / or Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

The present invention also provides the above-mentioned adhesive composition (I),
Applying to one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, forming a curable adhesive layer (II),
Next, the one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides is brought into contact and stuck to the curable adhesive layer (II) and / or brought into contact and stuck. Then, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

The present invention also provides the above-mentioned adhesive composition (I),
Applying to the surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided, forming the curable adhesive layer (II),
Next, on the curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board ( A plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit of 1) is not provided is brought into contact and stuck and / or heated after being brought into contact and stuck. It is related with the manufacturing method of the printed wiring board formed.

The present invention also provides the above-mentioned adhesive composition (I),
It is applied to the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface where no conductive circuit is provided, and a curable adhesive layer (II) is formed.
Then, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (II) and / or after making contact and sticking, The present invention relates to a method for manufacturing a flexible printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

Further, the present invention provides a curable adhesive layer (II) of the above adhesive sheet,
Contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet,
The surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface on the exposed curable adhesive layer (II) or the second single-sided printed wiring board. (1) While the surface where the conductive circuit is not provided is brought into contact with and / or stuck, and / or after being brought into contact and stuck,
Or
The curable adhesive layer (II) of the above adhesive sheet,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

Further, the present invention provides a curable adhesive layer (II) of the above adhesive sheet,
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Alternatively, the curable adhesive layer (II) of the above adhesive sheet,
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
The exposed curable adhesive layer (II) is brought into contact with and / or brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. The present invention relates to a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is carried out after pasting.

Further, the present invention provides a curable adhesive layer (II) of the above adhesive sheet,
One side printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet is peeled off,
After exposing and adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II) and / or after contacting and adhering, Heat or curable adhesive layer (II) of the above adhesive sheet,
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
Adhering the exposed surface of the curable adhesive layer (II), which is not provided with the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or Or it is related with the manufacturing method of the printed wiring board by which a several conductive circuit layer is laminated | stacked characterized by heating after making it contact and stick.

Further, the present invention provides a curable adhesive layer (II) of the above adhesive sheet,
Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
Adhering and / or adhering one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides to the exposed curable adhesive layer (II) Then, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

Furthermore, the present invention provides a curable adhesive layer (II) of the above adhesive sheet,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface is not provided in contact with the exposed curable adhesive layer (II), the surface is not attached. In addition, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contacting and sticking.

The adhesive composition of the present invention is excellent in adhesive strength to polyimide films, conductive circuits, and reinforcing materials, has good storage stability, and can provide a cured layer having excellent soldering heat resistance. It can be suitably used for laminating flexible printed wiring boards and mounting cover films for reinforcing materials and conductive circuit protection. Further, since the storage stability of the adhesive composition and the curable adhesive layer formed therefrom is excellent, there is little change in characteristics even after transport and storage processes under various conditions.
Further, the adhesive composition of the present invention can be stored at room temperature, such as an adhesive sheet using the same, a reinforcing agent with an adhesive layer for a flexible printed wiring board, or a cover film with an adhesive layer. Does not require low temperature storage.

It is typical sectional drawing of the flexible printed wiring board to which the reinforcing material with an adhesive layer was attached. It is typical sectional drawing of the flexible printed wiring board coat | covered with the cover film with an adhesive bond layer. It is a typical sectional view of a printed wiring board formed by laminating a plurality of conductive circuit layers. It is typical sectional drawing of a single-sided printed wiring board (1). It is typical sectional drawing of a double-sided printed wiring board (2).

Explanation of symbols

1: Base film 2: Conductive circuit 3: Reinforcement material 4: Cured adhesive layer (III)
5: Flexible printed circuit board 6: Plastic film (cover film)

First, the adhesive composition (I) of the present invention will be described.
The polyurethane polyurea resin (A) contained in the adhesive composition (I) is a urethane having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group. It is obtained by reacting a prepolymer (d), a polyamino compound (e), and a monoamino compound (f).

  In the present specification, the “polyol compound (a)” is a compound other than the carboxyl group-containing diol compound used as the component (c) described later, among the compounds generally known as the polyol component constituting a normal polyurethane resin. For example, various polyether polyols other than carboxyl group-containing diol compounds, polyester polyols, polycarbonate polyols, polybutadiene glycols, or a mixture thereof can be used.

  Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, or tetrahydrofuran.

  Examples of polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl- Saturated or unsaturated low-molecular diols such as 1,5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol, adipic acid, and phthalic acid , Diphthalic acids such as isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, or their anhydrides Obtained Reester polyols, n-butyl glycidyl ethers, alkyl glycidyl ethers of 2-ethylhexyl glycidyl ethers, monocarboxylic glycidyl esters such as versatic acid glycidyl esters and anhydrides of the above dicarboxylic acids And polyester polyols obtained by reacting in the presence of a hydroxyl group-containing compound such as, or polyester polyols obtained by ring-opening polymerization of a cyclic ester compound.

Examples of polycarbonate polyols include:
1) A reaction product of a diol or bisphenol and a carbonate ester, or 2) a reaction product obtained by reacting diol or bisphenol with phosgene in the presence of an alkali can be used.

  Examples of the carbonic acid ester used in the case of 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or propylene carbonate.

  Examples of the diol used in the case of 1) or 2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl. -1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1,1 -Dimethyl 2-hydroxyethyl, or 2,2,8,10- tetraoxospiro [5.5] undecane.

  Examples of the bisphenol used in the case of 1) or 2) include, for example, bisphenols such as bisphenol A and bisphenol F, and compounds obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to these bisphenols. Is mentioned.

  Examples of the alkali used in the case 2) include sodium hydroxide and potassium hydroxide.

  The number average molecular weight (Mn) of the polyol compound (a) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility, etc. of the obtained polyurethane polyurea resin (A), but the range of 1000 to 5000 is Preferably, it is 1000-4000. When Mn is less than 1000, the number of urethane bonds in the polyurethane polyurea resin (A) increases so much that the flexibility of the polymer skeleton tends to decrease and the adhesion to polyimide films and conductive circuits tends to decrease. When it exceeds 5000, the molecular weight between cross-linking points increases, and the solder heat resistance tends to decrease.

  The said polyol compound (a) may be used individually by 1 type, or may use 2 or more types together. Furthermore, within the range in which the adhesion performance of the polyurethane polyurea resin (A) is not lost, various kinds of low molecular diols, for example, a molecular weight of about 400 or less used for the production of the polyol compound as part of the polyol compound (a). Low molecular diols can be used instead.

As the organic diisocyanate compound (b), for example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.
Examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and the like.

  Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate.

  Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, or methylcyclohexane diisocyanate. Etc.

  Examples of the diol compound (c) having a carboxyl group include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylolpentanoic acid, dihydroxysuccinic acid, or dihydroxybenzoic acid. . In particular, dimethylolpropionic acid or dimethylolbutanoic acid is preferable from the viewpoint of reactivity or solubility.

The polyol compound (a), the organic diisocyanate (b), and the diol compound (c) having a carboxyl group are reacted to obtain a urethane prepolymer (d) having an isocyanate group. Regarding the total hydroxyl group of the diol compound (c) having a carboxyl group and the isocyanate group of the organic diisocyanate (b), the ratio of isocyanate group / hydroxyl group is within a range of 1.05 / 1 to 1.50 / 1 in molar ratio. It is preferable to make it react, More preferably, it is 1.10 / 1-1.45 / 1. When the molar ratio of isocyanate group / hydroxyl group is less than 1.05 / 1, the number of urea bonds contained in the polyurethane polyurea resin (A) may be small, and the film formability may be reduced, and when it exceeds 1.50 / 1, It is difficult to obtain a polyurethane polyurea resin having a weight average molecular weight necessary to exhibit sufficient solder heat resistance.
The ratio of the polyol compound (a) to the diol compound (c) having a carboxyl group is not particularly limited, but the molar ratio of the polyol compound (a) / carboxyl group-containing diol compound (c) is preferably 95 / It is in the range of 5-20 / 80, more preferably in the range of 90 / 10-35 / 65. When the molar ratio of the polyol compound (a) / carboxyl group-containing diol compound (c) exceeds 95/5, crosslinking between the polyurethane polyurea resin (A) and the epoxy resin (B) becomes too small and heat resistance decreases. In some cases, if it is less than 20/80, crosslinking between the polyurethane polyurea resin (A) and the epoxy resin (B) becomes excessive, and the adhesiveness may be lowered.

The reaction can be usually carried out at a temperature between room temperature and 150 ° C., and is preferably carried out between 60 and 120 ° C. from the viewpoint of production time or side reaction control.
The weight average molecular weight of the resulting isocyanate group-containing urethane prepolymer (d) is preferably in the range of 10,000 to 50,000, more preferably 12,000 to 40,000. When Mw is less than 10,000, it is difficult to obtain a polyurethane polyurea resin having a weight-average molecular weight necessary to exhibit sufficient solder heat resistance. When it exceeds 50,000, the viscosity of the adhesive composition is high. This is not preferable because the handleability is lowered.

The polyurethane polyurea resin (A) is obtained by reacting a urethane prepolymer (d) having an isocyanate group, a polyamino compound (e), and a monoamino compound (f).
The polyamino compound (e) serves as a chain extender, and is, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, or norbornanediamine. In addition, amines having a hydroxyl group such as 2- (2-aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, or di-2-hydroxypropylethylenediamine are also included. Can be used. Of these, isophoronediamine is preferably used.
The monoamino compound (f) serves as a molecular weight modifier for the polyurethane polyurea resin. For example, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol or isopropyl alcohol Can be used.

  The conditions for reacting the urethane prepolymer (d) having an isocyanate group, the polyamino compound (e), and the monoamino compound (f) are based on the amount of free isocyanate groups that the urethane prepolymer (d) has. In this case, it is important that the total molar ratio of the amino groups of the polyamino compound (e) and the monoamino compound (f) is in the range of 0.8 to 0.999, preferably 0.85 to 0.995. It is a range. When the total molar ratio of amino groups is less than 0.8, the molecular weight of the polyurethane polyurea resin cannot be made sufficiently high, so that the solder heat resistance is not sufficient. When the total molar ratio is more than 0.999, the polyamino compound (e) and the monoamino compound (f) are likely to remain unreacted and directly react with the epoxy resin in the adhesive composition, or the catalytic activity is increased. This is not preferable because it reduces the storage stability of the adhesive composition.

  Moreover, the amino group of a polyamino compound (e) is 90.0 mol%-97.0 mol% among the total 100 mol% of the amino group of a polyamino compound (e) and the amino group of a monoamino compound (f). Is important, preferably in the range of 92.0 mol% to 96.0 mol%. When the ratio of the amino group of the polyamino compound (e) is less than 90.0 mol%, it is difficult to obtain a polyurethane polyurea resin having a weight average molecular weight necessary to exhibit sufficient solder heat resistance. Moreover, when the ratio of the amino group of the polyamino compound (e) is more than 97.0 mol%, the viscosity of the adhesive composition is high and the handleability is deteriorated. Furthermore, the amino compound tends to remain unreacted as an amino compound. It is not preferable because it reacts directly with the epoxy resin in the agent composition or exhibits catalytic activity and lowers the storage stability of the adhesive composition.

  The weight average molecular weight (Mw) of the polyurethane polyurea resin (A) is important to be in the range of 80000 to 250,000, and preferably in the range of 90000 to 200000. When the weight average molecular weight is less than 80000, the solder heat resistance is inferior, and when it exceeds 250,000, the viscosity of the resin solution becomes high and the handleability is lowered, which is not preferable.

  The acid value of the polyurethane polyurea resin (A) needs to be in the range of 3 to 25 mgKOH / g, and preferably in the range of 7 to 20 mgKOH / g. In addition, an acid value is an acid value by a carboxyl group, and is with respect to solid content of a polyurethane polyurea resin (A). When the acid value of the polyurethane polyurea resin (A) is smaller than 3 mgKOH / g, crosslinking with the epoxy resin contained in the adhesive composition (I) becomes insufficient, and the heat resistance of the adhesive layer after curing is insufficient. Reduced solder heat resistance does not appear. Further, when the acid value is larger than 25 mgKOH / g, it is excessively cross-linked with the epoxy resin contained in the adhesive composition (I), and an adherend, for example, a plastic film such as a polyimide film, a glass epoxy plate, The peel strength to a metal plate etc. decreases.

The amine value of the polyurethane polyurea resin (A) is preferably in the range of 0 to 1.5 mgKOH / g, more preferably in the range of 0 to 1.2 mgKOH / g. The amine value referred to here is the number of mg of potassium hydroxide in the same mole as hydrochloric acid necessary to neutralize 1 g of the solid content of the polyurethane polyurea resin (A), and is unreacted contained in the polyurethane polyurea resin. In proportion to the amount of the polyamino compound (e) and the monoamino compound (f). When the amine value is larger than 1.5 mgKOH / g, the unreacted polyamino compound (e) and monoamino compound (f) react directly with the epoxy resin in the adhesive composition or show catalytic activity, and the adhesive The storage stability of the composition is lowered, which is not preferable.
The amine value is measured by the method shown below. That is, about 30 g of polyurethane polyurea resin solution was dissolved in a mixed solution of methanol / n-butanol / toluene = 40 mL / 20 mL / 40 mL, titrated with 0.1 N hydrochloric acid aqueous solution, Find the amount. The value obtained by converting the number of milligrams of potassium hydroxide in the same mole as hydrochloric acid contained in this aqueous hydrochloric acid solution per 1 g of polyurethane polyurea resin solid content was defined as the amine value (mgKOH / g).

  In addition, when the urethane prepolymer (d) having an isocyanate group is reacted with the polyamino compound (e) and the monoamino compound (f) (ureaization), the reaction temperature is appropriately adjusted so that the ureaization proceeds sufficiently. it can. In general, isocyanate groups and amino groups are said to react quantitatively even at a reaction temperature from about room temperature to about 50 ° C., but when obtaining a polyurethane polyurea resin having a weight average molecular weight specified in the present invention, it is higher. It is preferable that urea formation proceeds sufficiently at the reaction temperature. Preferably it is 70-100 degreeC, More preferably, it is 75 degreeC-95 degreeC. If the reaction temperature is less than 70 ° C., the urea-forming reaction is difficult to complete, and an unreacted amino compound decreases the storage stability of the adhesive composition. Moreover, when it exceeds 100 degreeC, an isocyanate group may react with functional groups other than an amino group, and is unpreferable.

When synthesizing the polyurethane polyurea resin (A), for example, a compound selected from an ester solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, a carbonate solvent, water, or the like One kind can be used alone, or two or more kinds can be used in combination as a solvent.
Examples of the ester solvent include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and ethyl lactate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone benzene, diisobutyl ketone, diacetone alcohol, isophorone, and cyclohexanone.

  Examples of the glycol ether solvent include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or these monoethers. And diethers such as diethylene glycol dimethyl ether or diethylene glycol diethyl ether.

Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
Examples of the aromatic solvent include toluene and xylene.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and cyclohexanol.
Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, or di-n-butyl carbonate.

  In addition, what has a hydroxyl group among the above-mentioned various solvents cannot be used when obtaining the urethane prepolymer (d) which has an isocyanate group. However, when the urethane prepolymer (d) having an isocyanate group, the polyamino compound (e), and the monoamino compound (f) are reacted (ureaized), a solvent having a hydroxyl group can be appropriately used. This is because the reaction between the amino group and the isocyanate group is much faster than the reaction between the hydroxyl group and the isocyanate group. When a urea bond is generated by a reaction between a hydroxyl group and an isocyanate group, a hydrogen bond is strengthened, so that the reaction solution becomes extremely high in viscosity. When a solvent having a hydroxyl group is used in the urea formation, the increase in the hydrogen bond can be alleviated.

  The epoxy resin (B) contained in the adhesive composition (I) of the present invention is a compound having an epoxy group, and may be liquid or solid, and is particularly limited. However, those having an average of two or more epoxy groups in one molecule can be preferably used. As the epoxy resin (B), for example, an epoxy resin such as a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic type) epoxy resin can be used.

  Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolak. Type epoxy resin, bisphenol A type novolac type epoxy resin, dicyclopentadiene type epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyloxyphenyl) Ethane and the like can be mentioned.

  Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, and tetraglycidylmetaxylylenediamine.

Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and the like.
Examples of the cycloaliphatic (alicyclic) epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, bis (epoxycyclohexyl) adipate, and the like.
As an epoxy resin (B), 1 type of the said compound can be used individually or in combination of 2 or more types.
As the epoxy resin (B), bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyloxyphenyl) are used from the viewpoint of high adhesion and heat resistance. It is preferred to use ethane.

  The adhesive composition (I) of the present invention preferably contains 5 to 100 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A), and contains 7 to 90 parts by weight. Is more preferable. When the amount of the epoxy resin (B) is less than 5 parts by weight, the solder heat resistance is hardly exhibited. When the amount of the epoxy resin (B) is more than 100 parts by weight, the adhesion to a plastic film such as a polyimide film or a conductive circuit tends to decrease.

  In the adhesive composition (I) used in the present invention, for the purpose of promoting the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) and the reaction between the epoxy resins (B), a curing accelerator and A curing agent can be contained. Examples of the curing accelerator for the epoxy resin (B) include tertiary amine compounds, phosphine compounds, or imidazole compounds, and examples of the curing agent include dicyandiamide, carboxylic acid hydrazide, and acid anhydrides.

  Examples of the tertiary amine compound as a curing accelerator include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, or 1,5-diazabicyclo (4.3.0) nonene. -5 and the like. Examples of the phosphine compound include triphenylphosphine or tributylphosphine. Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole. Examples include latent curing accelerators with improved storage stability, such as a type in which an imidazole compound and an epoxy resin are reacted to insolubilize in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule. Accelerators are preferred.

Examples of the carboxylic acid hydrazide as the curing agent include succinic acid hydrazide and adipic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride, trimellitic anhydride, and the like.
As these curing accelerators or curing agents, the above compounds may be used alone or in combination of two or more, and the content thereof is 0.1 in total with respect to 100 parts by weight of the epoxy resin (B). A range of ˜30 parts by weight is preferred.

The adhesive composition (I) of the present invention may contain a filler (C) for the purpose of improving solder heat resistance, thermal conductivity, or controlling the fluidity of the adhesive.
Examples of the filler (C) include silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorolinite, kaolin, or Examples thereof include inorganic fillers such as bentonite and metal fillers such as aluminum, gold, silver, copper, and nickel. Among these, silica, alumina, or aluminum hydroxide is preferable from the viewpoint of dispersibility. In particular, hydrophobic silica obtained by modifying a silanol group on the silica surface with a halogenated silane can reduce the water absorption rate and is suitably used for the adhesive composition of the present invention.

  The blending amount of the filler (C) is preferably 0.1 to 100 parts by weight, and more preferably 0.2 to 50 parts by weight with respect to 100 parts by weight of the polyurethane polyurea resin (A).

The adhesive composition (I) of the present invention includes a silane coupling agent, a heat stabilizer, a pigment, a dye, a tackifier resin, a plasticizer, and an ultraviolet absorber as long as the adhesive strength, heat resistance, and storage stability are not deteriorated. An agent, an antifoaming agent, a leveling adjusting agent, etc. can be mix | blended.
Furthermore, by using a heat stabilizer in combination, more excellent solder heat resistance can be imparted. As the heat stabilizer, for example, a hindered phenol, phosphorus (phosphite), lactone, hydroxylamine, or sulfur can be used, and a hindered phenol heat stabilizer is particularly effective. It is.

Next, the adhesive sheet of the present invention will be described.
The adhesive sheet of the present invention has a curable adhesive layer (II) composed of the adhesive composition (I) of the present invention on the peelable sheet, that is, an adhesive having an uncured adhesive layer (II). It is a sheet. The curable adhesive layer (II) carried on the first peelable sheet may be further coated with another peelable sheet (second peelable sheet), and thus the present invention. The adhesive sheet according to the present invention has a two-layer structure of peelable sheet / curable adhesive layer (II), or a three-layer structure of first peelable sheet / curable adhesive layer (II) / second peelable sheet. There is something.

  In either case of the first peelable sheet or the second peelable sheet, the peelable sheet is an adhesive to an adherend such as a flexible printed wiring board substrate, a glass epoxy board, or a stainless steel board (for example, a SUS board). When laminating the layer (II), it is not particularly limited as long as it can be peeled off from the adhesive layer. Silicone or a fluorine compound is applied to a plastic film such as polyester, polyolefin, polyimide, or polyamide, glassine paper, or polyethylene laminated fine paper. What coated the release agent containing can be used.

The adhesive layer (II) is formed on at least one surface of the peelable sheet by a conventionally known method such as knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spraying. After applying the adhesive composition (I) of the present invention by coating or spin coating, the adhesive composition (I) is not cured, that is, usually at 40 to 150 ° C. for 20 seconds to 60 minutes. Manufactured by drying.
Further, the dry film thickness of the curable adhesive layer (II) is preferably 5 μm to 500 μm, more preferably 10 μm from the viewpoint of ease of handling in order to exhibit sufficient adhesion and solder heat resistance. ˜100 μm.

Next, the reinforcing material with an adhesive layer for flexible printed wiring boards and the flexible printed wiring board with reinforcing materials of the present invention will be described.
The reinforcing material with an adhesive layer according to the present invention is obtained by forming a curable adhesive layer (II) formed from the above-described adhesive composition (I) of the present invention on a reinforcing material.
For example, the adhesive composition (I) is applied onto the reinforcing material by the method exemplified in the method for producing the peelable sheet, and then dried under the condition that the adhesive composition (I) is not cured. Thus, the curable adhesive layer (II) can be formed.

  The flexible printed wiring board used in the present invention is not particularly limited, for example, one having a conductive circuit on one surface, one having a conductive circuit on both surfaces, and one having a conductive circuit inside thereof. Etc. Further, the base film of the flexible printed wiring board is not particularly limited, and a suitable one is a plastic film having insulating properties, flexibility, and heat resistance. For example, polyimide, polyethylene terephthalate (PET), polyphenylene sulfide, poly Examples include ether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, wholly aromatic polyamide, and liquid crystal polymer represented by wholly aromatic polyester. As the copper foil, an electrolytic copper foil or a rolled copper foil can be used.

  Examples of the reinforcing material include glass epoxy plates, metal plates such as aluminum or stainless steel (for example, SUS), and plate-like members such as polyimide plates. The thickness of the reinforcing material may be a reinforcing function with respect to the flexible printed wiring board, and is preferably about 20 to 5000 μm.

  The flexible printed wiring board with a reinforcing material of the present invention is a glass epoxy board, a metal plate, a polyimide board, or the like using the adhesive composition (I) of the present invention or the adhesive sheet of the present invention for a flexible printed wiring board. These reinforcing materials are bonded and fixed by operations such as heat laminating, heat pressing, and / or heat curing alone or in combination.

  FIG. 1 is a cross-sectional view schematically showing the structure of one embodiment of a flexible printed wiring board with a reinforcing material of the present invention. That is, the flexible printed wiring board 10 with a reinforcing material includes a flexible printed wiring board 11 and a reinforcing material 12. The flexible printed wiring board 11 carries the conductive circuit 2 on one surface of the insulating base film 1. The reinforcing material 12 is bonded and fixed to a part of the surface (back surface) 11a of the base film 1 on the side opposite to the carrying surface of the conductive circuit 2 via the cured adhesive layer 4. The reinforcing material 12 can be fixed to the entire back surface 11a of the flexible printed wiring board 11.

The flexible printed wiring board with a reinforcing material can be obtained by various methods.
For example, after applying the adhesive composition (I) on the reinforcing material as described above and drying it to provide a curable adhesive layer (II) to prepare a reinforcing material with a curable adhesive layer, The curable adhesive layer (II) of the reinforcing material with the adhesive layer and the portion of the flexible printed wiring board where the conductive circuit is not provided are heated while being in contact with each other or heated after being adhered and adhered. The curable adhesive layer (II) can be cured to obtain the flexible printed wiring board with a reinforcing material of the present invention.
Alternatively, the adhesive composition (I) is applied to a portion of the flexible printed wiring board where the conductive circuit is not provided, and this is dried to provide the curable adhesive layer (II). The flexible printed wiring board with a reinforcing material of the present invention is cured by heating while bringing the reinforcing material into contact with the adhesive layer (II) or by heating after making it contact to cure the curable adhesive layer (II). It can also be obtained.

Moreover, the flexible printed wiring board with a reinforcing material can also be obtained using the adhesive sheet of this invention.
That is, the curable adhesive layer (II) of the adhesive sheet of the present invention having the curable adhesive layer (II) formed from the adhesive composition (I) on the peelable sheet is in contact with the reinforcing material. And then peeling off the peelable sheet and heating the exposed curable adhesive layer (II) in contact with the portion of the flexible printed wiring board where the conductive circuit is not provided, or heating after contacting,
Alternatively, the curable adhesive layer (II) of the adhesive sheet is brought into contact with the portion of the flexible printed wiring board where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the curable adhesive layer (II) exposed. It is also possible to obtain a flexible printed wiring board with a reinforcing material of the present invention by heating while contacting the reinforcing material, or by heating after contacting the reinforcing material to cure the curable adhesive layer (II).

Alternatively, one peel from the adhesive sheet of the present invention in which the curable adhesive layer (II) formed from the adhesive composition (I) on the peelable sheet and the other peelable sheet is further laminated thereon. The peelable sheet is peeled off, the exposed curable adhesive layer (II) is brought into contact with the reinforcing material, the other peelable sheet is then peeled off, and the exposed curable adhesive layer (II) is connected to the conductive circuit of the flexible printed wiring board. Or heating while in contact with the part where is not provided, or heating after contacting,
Alternatively, peel off one peelable sheet from the adhesive sheet, bring the exposed curable adhesive layer (II) into contact with the portion of the flexible printed wiring board where the conductive circuit is not provided, and then peel off the other peelable sheet The exposed curable adhesive layer (II) is heated while being in contact with the reinforcing material, or is heated after contacting the curable adhesive layer (II) to cure the curable adhesive layer (II). A wiring board can also be obtained.
In addition, the application method of adhesive composition (I) can illustrate similarly the method described in relation to the application method of an adhesive sheet.

  In any of the above cases, pressure can also be applied when and / or after attaching the reinforcing material on the flexible printed wiring board. More specifically, by passing between two heated rolls of a laminate composed of a flexible printed wiring board / curable adhesive layer (II) / reinforcing material, or hot pressing the laminate, A flexible printed wiring board and a reinforcing material can be bonded more firmly.

Moreover, after bonding a flexible printed wiring board and a reinforcing material, it can heat further and hardening of curable adhesive bond layer (II) can also be advanced.
For example, this curable adhesive layer (II) can be made into a cured adhesive layer (III) by heating at 100 to 200 ° C. for about 30 minutes to 24 hours. The film thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

  The flexible printed wiring board with a reinforcing material obtained as described above is in a state in which the flexible printed wiring board and the reinforcing material are laminated via the cured adhesive layer (III).

Next, the plastic film with a curable adhesive layer and the flexible printed wiring board with a cover film of the present invention will be described.
The plastic film with a curable adhesive layer of the present invention is preferably used for the production of a flexible printed wiring board with a cover film, and the adhesive of the present invention is provided between a plastic film not subjected to a release treatment and a protective film. The curable adhesive layer (II) formed from the composition (I) is sandwiched.

The plastic film with a curable adhesive layer of the present invention is obtained by applying the adhesive composition (I) to a plastic film or a protective film that has not been subjected to a release treatment by various methods, and then drying the adhesive composition (I). It can be obtained by forming (II) and superposing a protective film or a plastic film not subjected to release treatment on the curable adhesive layer (II).
As a method for applying the adhesive composition (I), the method exemplified in the method for producing the peelable sheet can be used, and this is similarly dried to form the curable adhesive layer (II). .

  The plastic film not subjected to the peeling treatment is a cover film for covering the conductive circuit of the flexible printed wiring board. Examples of the plastic film that has not been peeled include plastic films such as polyester, polyolefin, polyimide, and polyamide, and a polyimide film is preferred.

  In addition, the protective film here is for protecting the curable adhesive layer of the plastic film with a curable adhesive layer, and may be peeled or not peeled. That is, if the protective film can be peeled off from the plastic film with the curable adhesive layer when the conductive circuit of the flexible printed wiring board is covered with the plastic film with the curable adhesive layer, a special peeling treatment is performed. What is not necessary may be used, and various things can be used. As what has been subjected to release treatment, for example, a plastic film such as polyester, polyolefin, polyimide, or polyamide coated with a release agent containing silicone or a fluorine compound can be used.

  The flexible printed wiring board with a cover film of the present invention is a cured adhesive layer formed on the surface of the flexible printed wiring board having a conductive circuit on the surface thereof on the side of the conductive circuit from the adhesive composition (I) of the present invention. Through (III), it is coated with a plastic film that has not been peeled.

  FIG. 2 is a cross-sectional view schematically showing the structure of one embodiment of the flexible printed wiring board with a cover film of the present invention. That is, the flexible printed wiring board 20 with the cover film has a plastic film (cover film) 6 bonded and fixed to the surface of the flexible printed wiring board 5 carrying the conductive circuit 2 with the cured adhesive layer 4 interposed therebetween. Yes. The flexible printed wiring board 5 carries the conductive circuit 2 on one surface of the insulating base film 1 via the adhesive layer 4a.

Such a flexible printed wiring board with a cover film can be obtained by various methods.
For example, the protective film is peeled off from the plastic film with a curable adhesive layer of the present invention, and the exposed curable adhesive layer (II) is applied to the surface of the flexible printed wiring board having the conductive circuit on the surface on the conductive circuit side. The flexible printed wiring board with a cover film of the present invention can be obtained by heating while contacting, or heating after contacting, and curing the curable adhesive layer (II).

  In addition, the adhesive composition (I) of the present invention is applied on a plastic film that has not been subjected to a release treatment, dried to form a curable adhesive layer (II), and then the curable adhesive layer (II). With the cover film of the present invention, the curable adhesive layer (II) is cured by heating while contacting the surface of the flexible printed wiring board on the conductive circuit side or by heating after contacting the surface. A flexible printed wiring board can also be obtained.

Further, the adhesive composition (I) is applied to the surface of the flexible printed wiring board on the conductive circuit side and dried to form a curable adhesive layer (II), and then the curable adhesive layer (II ) Is heated in contact with a plastic film that has not been peeled, or heated after contact, to cure the curable adhesive layer (II), and the flexible printed wiring with a cover film of the present invention You can also get a board.
In addition, the application method of adhesive composition (I) can illustrate similarly the method described in relation to the application method of an adhesive sheet.

  In any of the above cases, pressure can also be applied when and / or after bonding the cover film and the surface of the flexible printed wiring board on the conductive circuit side. More specifically, a laminate comprising an unexfoliated plastic film / curable adhesive layer (II) / flexible printed wiring board is passed between two heated rolls, or the laminate is hot pressed. By doing so, the cover film can be more firmly attached to the flexible printed wiring board.

Moreover, after a cover film is affixed on a flexible printed wiring board, it can heat further and hardening of curable adhesive bond layer (II) can also be advanced.
For example, this curable adhesive layer (II) can be made into a cured adhesive layer (III) by heating at 100 to 200 ° C. for about 30 minutes to 24 hours. The film thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

  The cover printed flexible printed wiring board obtained as described above is in a state in which the cover film and the conductive circuit side of the flexible printed wiring board are bonded to each other through the cured adhesive layer (III).

Next, a printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention will be described.
The printed wiring board used for constituting each layer of the printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention has a conductive circuit only on one surface, and is conductive on both surfaces. And the like having an active circuit. Moreover, it is preferable to use a flexible printed wiring board using a flexible plastic film as an insulating substrate in order to reduce the thickness and weight and to provide flexibility.

  Next, the printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated will be described with reference to FIGS. The printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated includes a printed wiring board having a conductive circuit on one surface of an insulating substrate and a printed wiring board having a conductive circuit on both surfaces of the insulating substrate. And laminated using the adhesive composition (I). 4 shows a printed wiring board (hereinafter referred to as a single-sided printed wiring board) 41 having a conductive circuit 2 on one surface of a base film 1 as an insulating substrate, and FIG. 5 shows both of the base film 1 as an insulating substrate. The printed wiring board (henceforth a double-sided printed wiring board) 51 which has the conductive circuits 2 and 2 on the surface is shown.

  [1] in FIG. 3 shows that the surface on the conductive circuit side of the first single-sided printed wiring board 41 and the surface on the conductive circuit side of the second single-sided printed wiring board 41 are composed of the adhesive composition (I). FIG. 2 schematically shows a state in which they are bonded and laminated via a cured adhesive layer 4 formed from the above.

  [2] in FIG. 3 is a cured adhesive layer 4 in which one surface of the double-sided printed wiring board 51 and the surface of the single-sided printed wiring board 41 on the conductive circuit side are formed from the adhesive composition (I). 1 schematically shows a state in which they are bonded and laminated.

  [3] in FIG. 3 shows that the surface on the conductive circuit side of the first single-sided printed wiring board 41 and the surface of the second single-sided printed wiring board 41 on which no conductive circuit is provided are the adhesive composition. FIG. 2 schematically shows a state in which they are bonded and laminated through a cured adhesive layer 4 formed from (I).

  [4] in FIG. 3 is a cured adhesion in which one surface of the double-sided printed wiring board 51 and the surface of the single-sided printed wiring board 41 where no conductive circuit is provided are formed from the adhesive composition (I). The state which is bonded and laminated through the agent layer 4 is schematically shown.

  [5] in FIG. 3 is a cured adhesion in which one surface of the first double-sided printed wiring board 51 and one surface of the second double-sided printed wiring board 51 are formed from the adhesive composition (I). The state which is bonded and laminated through the agent layer 4 is schematically shown.

[6] in FIG. 3 indicates that the surface of the first single-sided printed wiring board 41 that is not provided with the conductive circuit is bonded to the surface of the second single-sided printed wiring board 41 that is not provided with the conductive circuit. FIG. 2 schematically shows a state of being laminated and laminated via a cured adhesive layer 4 formed from the agent composition (I).
In FIG. 3, depending on the type of printed wiring board to be laminated, there are cases where there is no adhesive layer between the insulating substrate (base film) and the conductive circuit of each printed wiring board, and there are cases where it exists. However, in FIGS. 3-5, illustration of the adhesive bond layer between the insulated substrate of a printed wiring board and a conductive circuit was abbreviate | omitted.

  The laminates of the embodiments of [1] to [6] in FIG. 3 can be laminated in any combination via the cured adhesive layer (III) to further form a multilayer laminate.

The printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention is a method using the adhesive sheet of the present invention, and a method of applying the adhesive composition (I) onto a printed wiring board for lamination. It can be obtained by various methods.

  First, a plurality of curable adhesive layers (II) made of the adhesive composition (I) on the peelable sheet, and further using the adhesive sheet of the present invention in which another peelable sheet is laminated thereon. A method for manufacturing a printed wiring board in which the conductive circuit layers are laminated will be described.

  One peelable sheet is peeled off from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with the conductive circuit side surface of the first single-sided printed wiring board 41, and then the other peelable sheet is attached. The surface of the second single-sided printed wiring board 41 is brought into contact with and stuck to the exposed curable adhesive layer (II) and / or stuck and then heated. By doing so, a printed wiring board having a plurality of conductive circuit layers in the stacked state of [1] in FIG. 3 can be obtained.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
One peelable sheet is peeled off from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with one surface of the double-sided printed wiring board 51, and then the other peelable sheet is peeled off to expose the curable composition. The adhesive layer (II) is heated by contacting and adhering the surface on the conductive circuit side of the single-sided printed wiring board 41 and / or contacting and adhering,
Alternatively, one peelable sheet is peeled off from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with the surface of the single-sided printed wiring board 41 on the conductive circuit side, and then the other peelable sheet is peeled off. It can be obtained by heating while making one surface of the double-sided printed wiring board 51 contact and stick to the exposed curable adhesive layer (II) and / or after making it contact and stick. .

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
One peelable sheet is peeled off from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with the conductive circuit side surface of the first single-sided printed wiring board 41, and then the other peelable sheet is attached. The surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided is brought into contact and stuck to the exposed and curable adhesive layer (II) and / or brought into contact. After heating,
Alternatively, one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the other The peelable sheet is peeled off, and the exposed curable adhesive layer (II) is brought into contact with and adhered to the surface of the second single-sided printed wiring board 41 on the conductive circuit side, and / or brought into contact. It can be obtained by heating after heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
One peelable sheet is peeled off from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with one surface of the double-sided printed wiring board 51, and then the other peelable sheet-like substrate is peeled off and exposed. The surface of the single-sided printed wiring board 41 where the conductive circuit is not provided is brought into contact with and / or stuck to the curable adhesive layer (II), and / or heated after being brought into contact with the curable adhesive layer (II),
Alternatively, one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the single-sided printed wiring board 41 where the conductive circuit is not provided, and then the other peelable sheet. The sheet is peeled off, and one surface of the double-sided printed wiring board 51 is brought into contact with and stuck to the exposed curable adhesive layer (II) and / or after being brought into contact and stuck, and then heated. Can be obtained by:

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
One peelable sheet is peeled from the adhesive sheet, the exposed curable adhesive layer (II) is brought into contact with one surface of the first double-sided printed wiring board 51, and then the other peelable sheet is peeled off and exposed. It can be obtained by heating the curable adhesive layer (II) while one surface of the second double-sided printed wiring board 51 is brought into contact with and / or stuck and then heated. it can.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
One peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the other peelable sheet is peeled off. The conductive sheet is peeled off, and the exposed surface of the curable adhesive layer (II) on which the conductive circuit of the second single-sided printed wiring board 41 is not provided is brought into contact with and / or stuck. It can be obtained by heating after being applied.

  The printed wiring board having a plurality of conductive circuit layers in the laminated state shown by [1] to [6] in FIG. 3 is obtained by applying the adhesive composition (I) of the present invention onto the printed wiring board. Can also be obtained.

  For example, the printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state [1] in FIG. 3 has an adhesive composition on the surface of the first single-sided printed wiring board 41 on the conductive circuit side. (I) is applied and dried to form a curable adhesive layer (II). The surface of the second single-sided printed wiring board 41 on the conductive circuit side is brought into contact with the curable adhesive layer (II). It can be obtained by heating while adhering and / or adhering.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
The adhesive composition (I) is applied to one surface of the double-sided printed wiring board 51, dried to form a curable adhesive layer (II), and single-sided printing is performed on the curable adhesive layer (II). While contacting and sticking the surface of the conductive circuit side of the wiring board 41 and / or after making it contact and sticking, heating,
Alternatively, the adhesive composition (I) is applied to the conductive circuit side of the single-sided printed wiring board 41 and dried to form a curable adhesive layer (II), and the curable adhesive layer (II) is applied to the curable adhesive layer (II). It can be obtained by heating while one surface of the double-sided printed wiring board 51 is brought into contact and stuck and / or after being brought into contact and stuck.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
The adhesive composition (I) is applied to the surface on the conductive circuit side of the first single-sided printed wiring board 41 and dried to form a curable adhesive layer (II), and the curable adhesive layer ( II), the surface on which the conductive circuit of the second single-sided printed wiring board 41 is not provided is brought into contact with and / or adhered and / or heated,
Alternatively, the adhesive composition (I) is applied to the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided and dried to form the curable adhesive layer (II), and the curing is performed. By making the conductive adhesive layer (II) contact the surface on the conductive circuit side of the second single-sided printed wiring board 41 and sticking it and / or heating it after making it contact and stick Obtainable.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
The adhesive composition (I) is applied to one surface of the double-sided printed wiring board 51, dried to form a curable adhesive layer (II), and single-sided printing is performed on the curable adhesive layer (II). While contacting and pasting the surface of the wiring board 41 where the conductive circuit is not provided, and / or after contacting and pasting, heating,
Alternatively, the adhesive composition (I) is applied to the surface of the single-sided printed wiring board 41 where the conductive circuit is not provided, and dried to form the curable adhesive layer (II). It can be obtained by heating the layer (II) while one surface of the double-sided printed wiring board 51 is brought into contact with and / or stuck to the layer (II).

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
The adhesive composition (I) is applied to one surface of the first double-sided printed wiring board 51 and dried to form a curable adhesive layer (II). It can be obtained by heating after making one surface of the second double-sided printed wiring board 51 contact and sticking and / or after making contact and sticking.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
The adhesive composition (I) is applied to the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and dried to form the curable adhesive layer (II). It is obtained by heating the adhesive layer (II) while contacting and adhering the surface of the second single-sided printed wiring board 41 where the conductive circuit is not provided and / or adhering it. be able to.
In addition, the application method of adhesive composition (I) can illustrate similarly the method described in relation to the application method of an adhesive sheet.

Furthermore, the printed wiring board having a plurality of conductive circuit layers uses the adhesive sheet of the present invention having a curable adhesive layer (II) made of the adhesive composition (I) on a peelable sheet. It can also be obtained.
For example, the printed wiring board formed by laminating a plurality of conductive circuit layers shown in [1] in FIG. 3 has a curable adhesive layer (II) on the adhesive sheet on the first side. Contact the surface of the printed circuit board 41 on the conductive circuit side, and then peel off the peelable sheet, and expose the surface of the second single-sided printed circuit board 41 on the conductive circuit side to the exposed curable adhesive layer (II). It can obtain by making it contact and sticking and / or heating after making it stick and making it contact.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
The curable adhesive layer (II) on the adhesive sheet is brought into contact with one surface of the double-sided printed wiring board 51, then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is exposed to the single-sided printed wiring. While contacting and sticking the surface of the conductive circuit side of the plate 41 and / or after contacting and sticking, heating,
Alternatively, the curable adhesive layer (II) on the adhesive sheet is brought into contact with the conductive circuit side surface of the single-sided printed wiring board 41, and then the peelable sheet is peeled off to expose the exposed curable adhesive layer (II). In addition, it can be obtained by heating while one surface of the double-sided printed wiring board 51 is brought into contact and stuck and / or after being brought into contact and stuck.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
The curable adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 on the conductive circuit side, and then the peelable sheet is peeled off to expose the exposed curable adhesive layer (II ), The surface on which the conductive circuit of the second single-sided printed wiring board 41 is not provided is brought into contact with and / or adhered and / or heated,
Alternatively, the adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the exposed curable adhesive. It can be obtained by heating the layer (II) while the surface on the conductive circuit side of the second single-sided printed wiring board 41 is brought into contact and stuck and / or after being brought into contact and stuck. it can.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
The adhesive layer (II) on the adhesive sheet is brought into contact with one surface of the double-sided printed wiring board 51, then the peelable sheet is peeled off, and the single-sided printed wiring board 41 is applied to the exposed curable adhesive layer (II). While contacting and pasting the surface where no conductive circuit is provided, and / or after contacting and pasting, heating,
Alternatively, the adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the exposed curable adhesive layer (II ), And one surface of the double-sided printed wiring board 51 is brought into contact and stuck, and / or is brought into contact and stuck, and then heated.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
The curable adhesive layer (II) on the adhesive sheet is brought into contact with one surface of the first double-sided printed wiring board 51, then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is It can be obtained by heating after making one surface of the second double-sided printed wiring board 51 contact and sticking and / or after making contact and sticking.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
The curable adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the exposed curable adhesive. Obtained by heating the layer (II) while contacting and adhering the surface of the second single-sided printed wiring board 41 where the conductive circuit is not provided and / or adhering and adhering. Can do.

In any of the above cases, pressure can also be applied when each printed wiring board is bonded and / or after the printed circuit boards are bonded. More specifically, by passing a laminate comprising a printed wiring board / curable adhesive layer (II) / printed wiring board between two heated rolls, or hot pressing the laminate. A printed wiring board obtained by laminating and laminating a plurality of conductive circuit layers more firmly can be obtained.
Moreover, after obtaining the printed wiring board by which several electroconductive circuit layers are laminated | stacked, it can heat further and hardening of curable adhesive bond layer (II) can also be advanced further.
For example, this curable adhesive layer (II) can be made into a cured adhesive layer (III) by heating at 100 to 200 ° C. for about 30 minutes to 24 hours. The film thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
By setting the number of the printed wiring boards to be laminated to two or more, a large number of printed wiring boards are laminated via the cured adhesive layer (III).

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, parts and% mean parts by weight and% by weight, Mn means number average molecular weight, and Mw means weight average molecular weight.

[Synthesis Example 1]
A polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol [Kuraray Co., Ltd.] was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. “Kuraray polyol P-2011”, Mn = 2040] 195.2 parts, 6.67 parts of dimethylolbutanoic acid, 40.7 parts of isophorone diisocyanate, and 70.0 parts of toluene were charged at 90 ° C. under a nitrogen atmosphere. Reaction was conducted for 250 hours, and 250 parts of toluene was added thereto, and an isocyanate group-containing urethane prepolymer [Mw = 21,000, an organic diisocyanate (b) with respect to a hydroxyl group derived from a polyol compound (a) and a diol compound (c) having a carboxyl group. ) Derived isocyanate group molar ratio 1.30] solution was obtained.
Next, the above isocyanate group-containing urethane prepolymer solution 506. in a mixture of 6.08 parts of isophoronediamine, 0.59 parts of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene. 3 parts were added, reacted at 85 ° C. for 4 hours, diluted with 63.0 parts of toluene and 27.0 parts of 2-propanol, and polyurethane polyurea resin [Mw = 110,000, acid value = 10.1 mgKOH / g In the urethane prepolymer (d) having an isocyanate group, the molar ratio of all amino groups to isocyanate groups is 0.993, the ratio of amino groups derived from the polyamino compound to all amino groups is 94.0 mol%, and the amine value is 0. .85 mg / KOH, solid content of about 25%] was obtained.

[Synthesis Examples 2-5, 7-9, 13 and 16]
Except having used the raw material shown in Table 1, it was made to react like the synthesis example 1, and the polyurethane polyurea resin solution A-2-A-5, A-7-A-9, A-13, and A-16 were made. Obtained. Properties of the obtained polyurethane polyurea resin were as shown in Table 2.

[Synthesis Example 6]
Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in the same reaction vessel as in Synthesis Example 1 [“Kuraray Polyol P-2011” manufactured by Kuraray Co., Ltd., Mn = 2040] 482.9 parts, 16.5 parts of dimethylolbutanoic acid, 100.6 parts of isophorone diisocyanate, and 70.0 parts of toluene were charged and reacted at 90 ° C. for 4 hours under a nitrogen atmosphere. To this was added 330.0 parts of toluene. Thus, an isocyanate group-containing urethane prepolymer solution was obtained. The properties of the resulting isocyanate group-containing urethane prepolymer were as shown in Table 2.

[Synthesis Example 10]
In a reaction vessel similar to Synthesis Example 1, 13.30 parts of dimethylolbutanoic acid, 140.0 parts of isophorone diisocyanate, and 200.0 parts of toluene were charged and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. 120 parts of N-dimethylacetamide was added to obtain a mixed solution of a product obtained by adding isophorone diisocyanate to the hydroxyl group of dimethylolbutanoic acid and isophorone diisocyanate.
Next, a product obtained by adding isophorone diisocyanate to the hydroxyl group of dimethylolbutanoic acid in a mixture of 74.46 parts of isophoronediamine, 12.56 parts of di-n-butylamine and 297 parts of 2-propanol, and isophorone diisocyanate Slowly add 426.0 parts of a mixed solution of the mixture, react at 50 ° C. for 2 hours, then 70 ° C. for 2 hours, and dilute with 63.0 parts of toluene and 27.0 parts of 2-propanol to obtain a polyurethane polyurea resin and polyurea. Solution A-10 in a mixture with resin was obtained. Properties of the resulting resin mixture were as shown in Table 2. In addition, since the solid content of A-10 was insoluble in tetrahydrofuran (THF), the weight average molecular weight was not measurable.

[Synthesis Example 11]
Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in the same reaction vessel as in Synthesis Example 1 [“Kuraray Polyol P-2011” manufactured by Kuraray Co., Ltd., Mn = 2040] 189.7 parts, 5.96 parts of dimethylolbutanoic acid, 29.3 parts of isophorone diisocyanate, and 35.0 parts of toluene were charged and reacted at 90 ° C. for 10 hours in a nitrogen atmosphere. -Dilution with 55.0 parts of propanol gave a solution A-11 of a polyurethane resin (Mw = 88,000, acid value = 10.0 mg KOH / g, amine value 0 mg / KOH, solid content about 45%).

[Synthesis Example 12]
Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in the same reaction vessel as in Synthesis Example 1 [“Kuraray Polyol P-2011” manufactured by Kuraray Co., Ltd., Mn = 2040] 189.2 parts, 5.94 parts of dimethylol butanoic acid, 29.8 parts of isophorone diisocyanate, and 35.0 parts of toluene were charged and reacted at 90 ° C. for 10 hours in a nitrogen atmosphere. -Dilution with 55.0 parts of propanol gave a solution A-12 of a polyurethane resin (Mw = 91,000, acid value = 10.0 mg KOH / g, amine value 0 mg / KOH, solid content about 45%).

[Synthesis Example 14]
Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in the same reaction vessel as in Synthesis Example 1 [“Kuraray Polyol P-2011” manufactured by Kuraray Co., Ltd., Mn = 2040] 190.1 parts, 6.80 parts of dimethylolbutanoic acid, 43.3 parts of isophorone diisocyanate, and 70.0 parts of toluene were charged and reacted at 90 ° C. for 4 hours under a nitrogen atmosphere. To this, 250 parts of toluene was added, An isocyanate group-containing urethane prepolymer solution was obtained.
Next, in the mixture of 7.96 parts of isophoronediamine, 0.91 part of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene, the above isocyanate group-containing urethane prepolymer solution 504. 1 part was added, reacted at 50 ° C. for 2 hours, then reacted at 70 ° C. for 2 hours, diluted with 63.0 parts of toluene and 27.0 parts of 2-propanol to obtain a polyurethane polyurea resin solution A-14. . Properties of the obtained polyurethane polyurea resin were as shown in Table 2.

[Synthesis Example 15]
A reaction was carried out in the same manner as in Synthesis Example 14 except that the raw materials shown in Table 1 were used to obtain a polyurethane polyurea resin solution A-15. Properties of the obtained polyurethane polyurea resin were as shown in Table 2.

In addition, the number average molecular weight (Mn) of a polyol compound, the weight average molecular weight (Mw) of a urethane prepolymer and a polyurethane polyurea resin are the number average molecular weight and weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, GPC measurement conditions are It is as follows.
Apparatus: Shodex GPC System-21 [manufactured by Showa Denko KK]
Column: A total of 3 columns, Shodex KF-802, KF-803L, KF-805L (manufactured by Showa Denko Co., Ltd.) are connected and used.
Solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Temperature: 40 ° C
Sample concentration: 0.2% by weight
Sample injection volume: 100 μL

In Table 1, the symbol which shows the kind of polyol compound (a) has the following meaning.
P-2011: Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol [“Kuraray polyol P-2011” manufactured by Kuraray Co., Ltd., Mn = 2040]
PTG-2000SN: polyoxytetramethylene glycol ["PTG-2000SN" manufactured by Hodogaya Chemical Co., Ltd., Mn = 2029]
CD220: Polyhexamethylene carbonate diol [manufactured by Daicel Chemical Industries, Ltd. “Placcel CD220, Mn = 1965”]

[Example 1]
Tetrakis (glycidyloxyphenyl) ethane [“Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 180 to 220 g / eq] with respect to 400 parts of the polyurethane polyurea resin solution A-1 obtained in Synthesis Example 1. 10 parts and 20 parts of a hydrophobic silica filler [“Nippil SS-50F” manufactured by Tosoh Silica Co., Ltd.] were mixed to obtain an adhesive composition.
This adhesive composition was applied to a polyimide film having a thickness of 75 μm so that the dry film thickness was 25 μm, and dried at 80 ° C. for 2 minutes to produce a polyimide reinforcing material on which a curable adhesive layer (II) was laminated. .
In addition, the adhesive composition was applied to a polyimide film having a thickness of 25 μm (Kapton 100H, manufactured by Toray Industries, Inc.) so that the dry film thickness was 25 μm, dried at 80 ° C. for 2 minutes, and a protective film on the pressure-sensitive adhesive surface. (PET film peel-treated with silicone) was bonded together to produce a cover film with a curable adhesive layer.
Furthermore, the above adhesive composition is applied and dried on a polyester film which has been subjected to a release treatment so that the dry film thickness is 25 μm, to form a curable adhesive layer (II), and another release-treated polyester. The film was laminated to produce an adhesive sheet in which the curable adhesive layer (II) was sandwiched between peelable sheet-like substrates.

[Examples 2-5, Comparative Examples 1-2, 5-12, 14-16]
Adhesive composition, polyimide with curable adhesive layer (II) in exactly the same manner as in Example 1 except that the polyurethane polyurea resin solution, epoxy resin, and filler of the types and amounts shown in Table 3 were used. A reinforcing material, a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

[Comparative Example 3]
Carboxyl group-containing nitrile butadiene rubber [“NIPOL 1072J” manufactured by Nippon Zeon Co., Ltd., bound acrylonitrile amount 27.0%, Mooney viscosity 48] 100 parts, bisphenol A type epoxy resin [“Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd. ”, Epoxy equivalent = 189 g / eq] 200 parts, anhydrous silica filler [Nippon Aerosil Co., Ltd.“ Aerosil 300 ”] 2 parts finely pulverized dicyandiamide [Japan Epoxy Resin Co., Ltd.“ Epicure DICY7 ”] 14 parts , And 2 parts of an imidazole-based curing accelerator (“Amure PN-40” manufactured by Ajinomoto Fine Techno Co., Ltd.) were dissolved in toluene so as to have a solid content of 30% to prepare an adhesive composition. . Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were produced in exactly the same manner as in Example 1.

[Comparative Example 4]
In a reaction apparatus similar to Synthesis Example 1, 95.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 163.0 parts of ethyl acetate, and 0.06 part of 2,2′-azobisisobutyronitrile were charged, After the air in the reaction vessel was replaced with nitrogen gas, the reaction solution was heated to 80 ° C. and reacted for 9 hours in a nitrogen atmosphere with stirring. After completion of the reaction, 57 parts of toluene was added to obtain an acrylic resin solution having a solid content of 30.0%.
In 133 parts of this acrylic resin solution, 10 parts of bisphenol A type epoxy resin “Epicoat 828”, 0.1 part of silica filler “Aerosil 300”, 0.7 parts of finely pulverized dicyandiamide “Epicure DICY7”, and imidazole curing accelerator 0.1 part of “Amicure PN-40” was blended to obtain an adhesive composition. Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were produced in exactly the same manner as in Example 1.

[Comparative Example 5]
For 167 parts of the urethane prepolymer resin solution obtained in Synthesis Example 6, 20 parts of bisphenol A type epoxy resin ["Epicoat 1001" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 450 to 500 g / eq], Diaminodiphenyl sulfone [Wakayama Seika Kogyo Co., Ltd. “Seika Cure-S”] 8 parts and hydrophobic silica filler [Tosoh Silica Co., Ltd. “Nipsil SS-50F”] 30 parts were mixed to prepare an adhesive composition. Produced. Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were produced in exactly the same manner as in Example 1.

[Comparative Example 13]
Tetrakis (glycidyloxyphenyl) ethane [“Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 180 to 220 g / eq] with respect to 400 parts of the polyurethane polyurea resin solution A-13 obtained in Synthesis Example 13 10 parts, 2.5 parts of isophoronediamine, and 20 parts of hydrophobic silica filler [“Nippil SS-50F” manufactured by Tosoh Silica Co., Ltd.] were mixed to obtain an adhesive composition.
This adhesive composition was applied to a polyimide film having a thickness of 75 μm so that the dry film thickness was 25 μm, and dried at 80 ° C. for 2 minutes to produce a polyimide reinforcing material on which a curable adhesive layer (II) was laminated. .
In addition, the adhesive composition was applied to a polyimide film having a thickness of 25 μm (Kapton 100H, manufactured by Toray Industries, Inc.) so that the dry film thickness was 25 μm, dried at 80 ° C. for 2 minutes, and a protective film on the pressure-sensitive adhesive surface. (PET film peel-treated with silicone) was bonded together to produce a cover film with a curable adhesive layer.
Furthermore, the above adhesive composition is applied and dried on a polyester film which has been subjected to a release treatment so that the dry film thickness is 25 μm, to form a curable adhesive layer (II), and another release-treated polyester. The film was laminated to produce an adhesive sheet in which the curable adhesive layer (II) was sandwiched between peelable sheet-like substrates.

[Comparative Example 17]
Example 1 except that an isocyanurate body of hexamethylene diisocyanate (“Sumidule N3300” NCO% = 21.8%, manufactured by Sumika Bayer Urethane Co., Ltd.) was used in place of the epoxy resin as a crosslinking agent. In exactly the same manner, an adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

[Comparative Example 18]
Implemented except that alkylated melamine resin ["Cymel 303" manufactured by Mitsui Cytec Co., Ltd.] and curing catalyst [Catalyst 600 (0.5 phr for melamine resin)] was used as a crosslinking agent instead of epoxy resin. In exactly the same manner as in Example 1, an adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

[Comparative Example 19]
Adhesive composition in exactly the same manner as in Example 1 except that Tris-2,4,6- (1-aziridinyl) -1,3,5-triazine was used as the crosslinking agent instead of the epoxy resin. A polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

[Comparative Example 20]
Adhesive composition, polyimide reinforcing material with curable adhesive layer (II), cover film with curable adhesive layer, and adhesive exactly as in Example 1 except that Epicoat 1031S which is an epoxy resin is not used A sheet was produced.

In Table 3, the abbreviations indicating the types of the crosslinking agent other than the epoxy resin (B), the filler (C), and the epoxy resin have the following meanings.
EP1031S: Tetrakis (glycidyloxyphenyl) ethane, “Epicoat 1031S” manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent = 180-220 g / eq
EP152: Phenol novolac type epoxy resin, “Epicoat 152” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 172 to 178 g / eq
EP828: Bisphenol A type epoxy resin, “Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 189 g / eq
SS-50F: Hydrophobic silica filler, “Nippil SS-50F” manufactured by Tosoh Silica Corporation
R972: Hydrophobic silica filler, “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd.
TAT: Tris-2,4,6- (1-aziridinyl) -1,3,5-triazine

[Evaluation of the physical properties]
The following tests were conducted using the adhesive compositions, polyimide reinforcing materials with curable adhesive layers, cover films with curable adhesive layers, and adhesive sheets obtained in Examples and Comparative Examples.
(1) Polyimide reinforcing material with curable adhesive layer (1-1) Adhesive strength to polyimide film The curable adhesive layer side of the polyimide reinforcing material with curable adhesive layer (II) and another polyimide film (film Is laminated using a thermal laminator with a roll temperature of 100 ° C, and then heat-pressed under conditions of 150 ° C, 1.0MPa and 2min, and heated in an electric oven at 150 ° C for 180min to reinforce the polyimide. A laminate of material / cured adhesive layer (III) / polyimide film was prepared. This laminate was cut to a width of 10 mm, and a 90 ° peel peel test was conducted at 23 ° C. and 50% relative humidity at a pulling speed of 50 mm / min to determine the adhesive strength (N / cm).

(1-2) Adhesive strength to aluminum plate Adhesive layer side of polyimide reinforcing material with curable adhesive layer (II) and aluminum plate (thickness 100 μm, caustic treatment completed) are heated laminator with roll temperature of 100 ° C. After using and bonding, heat press under conditions of 150 ° C., 1.0 MPa, 2 min, and heat for 180 min in an electric oven at 150 ° C. to laminate polyimide reinforcing material / cured adhesive layer (III) / aluminum plate The body was made. This laminate was cut into a width of 10 mm, and a 180 ° peel peel test was performed at an pulling rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity to obtain an adhesive strength (N / cm).

(1-3) Adhesive strength after storage stability test A protective film (peeled PET film) was bonded to the curable adhesive layer of the polyimide reinforcing material with curable adhesive layer (II) described above, After leaving in a thermostatic bath for 30 days, the protective film is peeled off, and the curable adhesive layer side and another polyimide film (film thickness 75 μm) are bonded together using a thermal laminator with a roll temperature of 100 ° C., and then 150 The laminate was heat-pressed under the conditions of ° C., 1.0 MPa, and 2 min and heated in an electric oven at 150 ° C. for 180 min to prepare a polyimide reinforcing material / cured adhesive layer (III) / polyimide film laminate.
This laminate was cut to a width of 10 mm, and a 90 ° peel peel test was conducted at 23 ° C. and 50% relative humidity at a pulling speed of 50 mm / min to determine the adhesive strength (N / cm) after the storage stability test. Asked.

(1-4) Solder heat resistance after humidification The laminate for measuring the adhesive strength to the aluminum plate [polyimide reinforcing material / cured adhesive layer (III) / aluminum plate laminate] was cut to a width of 10 mm. Then, it was immersed in purified water at 85 ° C. for 3 hours, and the polyimide reinforcing material side was immediately brought into uniform contact with molten solder at 260 ° C. for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was evaluated.
○: No adhesion abnormality.
Δ: Some adhesion abnormality is observed.
X: Adhesion abnormality occurred.
The test results are shown in Table 4.

(2) Cover film with curable adhesive layer (2-1) Adhesive strength to roughened copper surface The protective film of the cover film with curable adhesive layer is peeled off, and the curable adhesive layer is made of an electrolytic copper foil having a thickness of 35 μm. Affixed to the mat surface using a heat laminator with a roll temperature of 100 ° C, then hot-pressed under conditions of 150 ° C, 1.0 MPa, 2 min, and further heated for 180 min in an electric oven at 150 ° C, with a cover film An electrolytic copper foil was produced.
The electrolytic copper foil with the cover film is cut to a width of 10 mm, and a 180 ° peel peel test is performed between the cover film and the electrolytic copper foil at a tensile rate of 50 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%. The adhesive strength (N / cm) was determined.

(2-2) Solder heat resistance after humidification The above-mentioned electrolytic copper foil with a cover film is cut with a width of 10 mm and immersed in purified water at 85 ° C. for 3 hours, and immediately the cover film side is melted at 260 ° C. Contacted for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was observed.
○: No adhesion abnormality.
Δ: Some adhesion abnormality is observed.
X: Adhesion abnormality occurred.

(2-3) Pattern embedding after storage stability test Flexible in which a protective film was peeled off from a cover film with a curable adhesive layer left in a constant temperature bath at 40 ° C. for 30 days, and a comb-shaped conductor pattern was formed by a subtractive method A curable adhesive layer was bonded to a copper clad laminate (line / space 0.1 mm) using a thermal laminator with a roll temperature of 100 ° C, and then hot pressed under conditions of 150 ° C, 1.0 MPa, and 2 min. And heated for 180 minutes in an electric oven at 150 ° C. to obtain a flexible copper-clad laminate having a comb-shaped conductor pattern with a cover film. The filling property of the cover film adhesive layer into the comb-shaped conductor pattern portion was visually observed to check for the presence of voids.
○: No void.
Δ: Slight voids are observed.
X: Many voids are observed.

(2-4) Change of insulation resistance A protective film is peeled off from a cover film with a curable adhesive layer, and a flexible copper-clad laminate (line / space 0.1 mm) formed with a comb-type conductor pattern by a subtractive method is rolled. After laminating a curable adhesive layer using a thermal laminator at a temperature of 100 ° C, it is hot pressed under the conditions of 150 ° C, 1.0 MPa and 2 min, and heated in an electric oven at 150 ° C for 180 min, with a cover film A flexible copper-clad laminate with a comb-shaped conductor pattern was obtained. A flexible copper-clad laminate having a comb-shaped conductor pattern with a cover film was applied with a voltage of 24 V and 1000 Hrs between the comb-shaped conductors in an atmosphere of 85 ° C. and 85% RH (relative humidity). The resistance values between the comb-shaped conductors before and after voltage application in a humidified atmosphere were compared.
○: Ra / Rb ≦ 10
Δ: Ra / Rb> 10
(Here, Ra represents a resistance value before voltage application, and Rb represents a resistance value after voltage application.)
The test results are shown in Table 5.

(3) Adhesive sheet (3-1) Adhesive strength to roughened copper surface Both peelable sheet-like substrates of the adhesive sheet (adhesive layer thickness 25 μm) are peeled off, and the curable adhesive layer is 35 μm thick. Between the matte surface of the electrolytic copper foil and a polyimide film (Kapton 200EN) having a thickness of 50 μm, heat-laminated at a roll temperature of 100 ° C., and then hot-pressed under conditions of 150 ° C., 1.0 MPa, 2 min. The laminate was heated for 180 minutes in an electric oven at 150 ° C. to obtain a laminate comprising electrolytic copper foil mat surface / cured adhesive layer (III) / polyimide film.
This laminate was cut into a width of 10 mm, and a 180 ° peel peel test was performed at an pulling rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity to obtain an adhesive strength (N / cm).

(3-2) Adhesive strength to copper glossy surface Both peelable sheet-like substrates of the adhesive sheet (adhesive layer thickness 25 μm) are peeled off, and the curable adhesive layer is a glossy surface of electrolytic copper foil having a thickness of 35 μm. And a 50 μm thick polyimide film (Kapton 200EN), heat-laminated at a roll temperature of 100 ° C., then hot-pressed under conditions of 150 ° C., 1.0 MPa and 2 min, and further 180 minutes in an electric oven at 150 ° C. It heated and the laminated body which consists of a glossy surface of electrolytic copper foil / cured adhesive layer (III) / polyimide film was obtained.
This laminate was cut into a width of 10 mm, and a 180 ° peel peel test was performed at an pulling rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity to obtain an adhesive strength (N / cm).

(3-3) Solder heat resistance after humidification The laminate made of the above-mentioned electrolytic copper foil mat surface / cured adhesive layer (III) / polyimide film is cut to a width of 10 mm, and purified water at 85 ° C. 3 It was immersed for a period of time, and the polyimide film side was immediately brought into contact with molten solder at 260 ° C. for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was observed.
○: No adhesion abnormality.
Δ: Some adhesion abnormality is observed.
X: Adhesion abnormality occurred.

(3-4) Pattern embedding after storage stability test Both peelable sheet-like substrates of the adhesive sheet (adhesive layer thickness 25 μm) left for 30 days in a constant temperature bath at 40 ° C. are peeled off and subtractive. A curable adhesive layer is sandwiched between a flexible copper-clad laminate (line / space 0.1 mm) having a comb-shaped conductor pattern formed by the method and a polyimide film (Kapton 200EN) having a thickness of 50 μm, and a roll temperature of 100 ° C. After heat laminating, hot pressing was performed under conditions of 150 ° C., 1.0 MPa, 2 min, and heating was performed for 180 min in an electric oven at 150 ° C. to obtain a flexible copper-clad laminate having a comb-shaped conductor pattern with a polyimide film. . The filling property of the adhesive layer into the comb-shaped conductor pattern was visually observed to check for the presence of voids.
○: No void.
Δ: Slight voids are observed.
X: Many voids are observed.

(3-5) Chemical resistance The adhesive composition (I) obtained in each Example and Comparative Example was applied to a tin plate so that the dry film thickness was 50 μm, and 180 minutes in an electric oven at 150 ° C. It was cured by heating, and the cured film was isolated by the mercury amalgam method. The cured film was visually observed for appearance after being immersed in a 10% NaOH aqueous solution and a 10% hydrochloric acid aqueous solution for 24 hours and after being immersed in acetone for 3 hours to evaluate whether there was swelling or dissolution.
○: No change.
Δ: A slight change is observed.
X: A clear change is observed.
The test results are shown in Table 6.

The adhesive composition of the present invention can be suitably used for laminating flexible printed wiring boards and mounting a cover film for protecting a reinforcing material and a conductive circuit.
As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (36)

Urethane prepolymer (d) having an isocyanate group obtained by reacting polyol compound (a), organic diisocyanate (b) and diol compound (c) having a carboxyl group, polyamino compound (e) and monoamino compound (f) And a polyurethane polyurea resin (A) and an epoxy resin (B) having a weight average molecular weight of 80000 to 250,000 and an acid value of 3 to 25 mgKOH / g, which are obtained by the reaction under the following conditions: An adhesive composition (I).
(I) The ratio of the isocyanate group of the urethane prepolymer (d) having an isocyanate group to the amino group of the polyamino compound (e) and the monoamino compound (f) is amino group / isocyanate group = 0.8 / 1 to 0. 999/1 (molar ratio),
And,
(Ii) The ratio of the amino group of the polyamino compound (e) is 90.0 to 97.0 mol% in the total of 100 mol% of the amino group of the polyamino compound (e) and the amino group of the monoamino compound (f). .   In the urethane prepolymer (d) having an isocyanate group, the ratio of the hydroxyl group of the polyol compound (a) and the diol compound (c) having a carboxyl group to the isocyanate group of the organic diisocyanate (b) is isocyanate group / hydroxyl group = 1. The adhesive composition (I) according to claim 1, which is reacted in a range of .05 / 1 to 1.50 / 1 (molar ratio).   The adhesive composition (I) according to claim 1 or 2, wherein the polyurethane polyurea resin (A) has an amine value of 0 to 1.5 mgKOH / g.   The number average molecular weight of the polyol compound (a) is 1,000 to 5,000, and the weight average molecular weight of the urethane prepolymer (d) is 10,000 to 50,000. The adhesive composition (I) described   The adhesive composition (I) according to any one of claims 1 to 4, comprising 5 to 100 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A). .   The adhesive composition (I) according to any one of claims 1 to 5, comprising a filler (C).   The adhesive composition (I) according to claim 6, comprising 0.1 to 100 parts by weight of the filler (C) with respect to 100 parts by weight of the polyurethane polyurea resin (A).   The adhesive sheet which has curable adhesive bond layer (II) which consists of adhesive composition (I) as described in any one of Claims 1-7 on a peelable sheet.   The adhesive sheet according to claim 8, further comprising another peelable sheet on the curable adhesive layer (II).   A reinforcing material with an adhesive layer for a flexible printed wiring board, having a curable adhesive layer (II) formed from the adhesive composition (I) according to any one of claims 1 to 7 on the reinforcing material. .   Through the cured adhesive layer (III) formed from the adhesive composition (I) according to any one of claims 1 to 7, in a portion where the conductive circuit of the flexible printed wiring board is not provided. A flexible printed wiring board with a reinforcing material, wherein the reinforcing material is fixed.   A method for producing a flexible printed wiring board with a reinforcing material, wherein the reinforcing material is fixed to the flexible printed wiring board using the adhesive sheet according to claim 8 or 9.   The adhesive composition (I) according to any one of claims 1 to 7 is applied on a reinforcing material to provide a curable adhesive layer (II), and then the curable adhesive layer (II). A flexible printed wiring board with a reinforcing material, wherein the flexible printed wiring board is heated while being brought into contact with and / or stuck to a portion where the conductive circuit of the flexible printed wiring board is not provided. Manufacturing method.   A curable adhesive layer (II) made of the adhesive composition (I) according to any one of claims 1 to 7 is sandwiched between a plastic film that has not been subjected to a peeling treatment and a protective film. Plastic film with adhesive layer.   A cured adhesive layer (III) formed from the adhesive composition (I) according to any one of claims 1 to 7, wherein the surface of the flexible printed wiring board having a conductive circuit on the surface thereof is on the conductive circuit side. A flexible printed wiring board with a cover film, which is covered with a plastic film that has not been subjected to a release treatment.   A protective film is peeled off from the plastic film with an adhesive layer according to claim 14, and the exposed curable adhesive layer (II) is brought into contact with the surface on the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface. A method for producing a flexible printed wiring board with a cover film, which is heated while being adhered and / or contacted and adhered.   The adhesive composition (I) according to any one of claims 1 to 7 is applied to one surface of an unpeeled plastic film to form a curable adhesive layer (II), and then Heating the curable adhesive layer (II) while the surface on the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface is brought into contact with and / or stuck and brought into contact. A method for producing a flexible printed wiring board with a cover film, comprising:   The adhesive composition (I) according to any one of claims 1 to 7 is applied to the surface on the conductive circuit side of a flexible printed wiring board having a conductive circuit on the surface, and a curable adhesive layer ( II) is formed, and then the curable adhesive layer (II) is heated while being brought into contact with and / or stuck to a plastic film that has not been subjected to a release treatment, and / or after being brought into contact with and stuck. The manufacturing method of the flexible printed wiring board with a cover film to do. Through the cured adhesive layer (III) formed from the adhesive composition (I) according to any one of claims 1 to 7,
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. Whether the surface of the conductive circuit is attached or
Is one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides and the surface on the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface? ,
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. Is it bonded to the surface where the conductive circuit is not provided?
One surface of the double-sided printed wiring board (2) having a conductive circuit on both sides and the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are not provided. Or
Whether one surface of the first double-sided printed wiring board (2) having the conductive circuit on both sides and one surface of the second double-sided printed wiring board (2) having the conductive circuit on both sides are bonded together Or
A surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, where no conductive circuit is provided, and a second single-sided printed wiring board having a conductive circuit only on one surface ( 1) A printed wiring board formed by laminating a plurality of conductive circuit layers, which is bonded to a surface on which a conductive circuit is not provided. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface is not attached to the exposed curable adhesive layer (II), the surface is not attached. And / or heating after contacting and sticking,
Or
One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the other peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Or
One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
The exposed curable adhesive layer (II) is brought into contact with and / or brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after pasting. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
Contact with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, where the conductive circuit is not provided, and then peel off the other peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Or
One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
Adhering to the exposed curable adhesive layer (II) with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface not provided with the conductive circuit, and / or Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet,
Adhering and / or adhering one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides to the exposed curable adhesive layer (II) And then heating the printed wiring board, wherein a plurality of conductive circuit layers are laminated. One peelable sheet is peeled from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the other peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface is not attached to the exposed curable adhesive layer (II), the surface is not attached. And / or heating after contacting and sticking, and a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated. The adhesive composition (I) according to any one of claims 1 to 7,
Applying to the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, forming a curable adhesive layer (II),
Next, on the curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board ( 1) A plurality of conductive circuit layers, wherein a surface not provided with a conductive circuit is contacted and adhered and / or heated after contacting and pasting, is laminated A printed wiring board manufacturing method. The adhesive composition (I) according to any one of claims 1 to 7,
It is applied to the surface on the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and a curable adhesive layer (II) is formed.
Then, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (II) and / or after making contact and sticking, Heating or
Or
The adhesive composition (I) according to any one of claims 1 to 7,
Apply to one surface of double-sided printed wiring board (2) with conductive circuit on both sides to form curable adhesive layer (II),
Next, the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface is brought into contact with and / or adhered to the curable adhesive layer (II). A method for producing a flexible printed wiring board in which a plurality of conductive circuit layers are laminated, the method comprising heating after pasting. The adhesive composition (I) according to any one of claims 1 to 7,
Apply to one surface of double-sided printed wiring board (2) with conductive circuit on both sides to form curable adhesive layer (II),
Next, the surface of the single-sided printed wiring board (1) having a conductive circuit on only one surface thereof, on which the conductive circuit is not provided, is brought into contact with and adhered to the curable adhesive layer (II) and / or Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. The adhesive composition (I) according to any one of claims 1 to 7,
Applying to one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, forming a curable adhesive layer (II),
Next, the one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides is brought into contact and stuck to the curable adhesive layer (II) and / or brought into contact and stuck. And then heating the printed wiring board, wherein a plurality of conductive circuit layers are laminated. The adhesive composition (I) according to any one of claims 1 to 7,
Applying to the surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided, forming the curable adhesive layer (II),
Next, on the curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board ( A plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit of 1) is not provided is brought into contact and stuck and / or heated after being brought into contact and stuck. A method for producing a printed wiring board. The adhesive composition (I) according to any one of claims 1 to 7,
It is applied to the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface where no conductive circuit is provided, and a curable adhesive layer (II) is formed.
Then, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (II) and / or after making contact and sticking, A method for producing a flexible printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. The curable adhesive layer (II) of the adhesive sheet according to claim 8,
Contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet,
The surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface on the exposed curable adhesive layer (II) or the second single-sided printed wiring board. (1) While the surface where the conductive circuit is not provided is brought into contact with and / or stuck, and / or after being brought into contact and stuck,
Or
The curable adhesive layer (II) of the adhesive sheet according to claim 8,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the peelable sheet is peeled off,
The exposed curable adhesive layer (II) is adhered to the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, and / or attached. Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. The curable adhesive layer (II) of the adhesive sheet according to claim 8,
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating or
Alternatively, the curable adhesive layer (II) of the adhesive sheet according to claim 8,
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
The exposed curable adhesive layer (II) is brought into contact with and / or brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after pasting. The curable adhesive layer (II) of the adhesive sheet according to claim 8,
One side printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet is peeled off,
After exposing and / or adhering one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides to the exposed curable adhesive layer (II), and / or Heating, or the curable adhesive layer (II) of the adhesive sheet according to claim 8,
Contact with one surface of the double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
Adhering to the exposed curable adhesive layer (II) with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface not provided with the conductive circuit, and / or Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. The curable adhesive layer (II) of the adhesive sheet according to claim 8,
Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the peelable sheet,
Adhering and / or adhering one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides to the exposed curable adhesive layer (II) And then heating the printed wiring board, wherein a plurality of conductive circuit layers are laminated. The curable adhesive layer (II) of the adhesive sheet according to claim 8,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface not provided with the conductive circuit, and then the peelable sheet is peeled off,
While the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface is not attached to the exposed curable adhesive layer (II), the surface is not attached. And / or heating after contacting and sticking, and a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated.

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